US2595334A - Benzothiazolesulfonamides and method of preparing the same - Google Patents
Benzothiazolesulfonamides and method of preparing the same Download PDFInfo
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- US2595334A US2595334A US154884A US15488450A US2595334A US 2595334 A US2595334 A US 2595334A US 154884 A US154884 A US 154884A US 15488450 A US15488450 A US 15488450A US 2595334 A US2595334 A US 2595334A
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- 238000000034 method Methods 0.000 title description 9
- SDYMYAFSQACTQP-UHFFFAOYSA-N 1,3-benzothiazole-2-sulfonamide Chemical class C1=CC=C2SC(S(=O)(=O)N)=NC2=C1 SDYMYAFSQACTQP-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 102000003846 Carbonic anhydrases Human genes 0.000 description 5
- 108090000209 Carbonic anhydrases Proteins 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229940124530 sulfonamide Drugs 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- 230000029142 excretion Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003456 sulfonamides Chemical class 0.000 description 3
- HSILAFDVJZUQPI-UHFFFAOYSA-N 1,3-benzothiazole-2-sulfonyl chloride Chemical compound C1=CC=C2SC(S(=O)(=O)Cl)=NC2=C1 HSILAFDVJZUQPI-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 206010030113 Oedema Diseases 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229950003476 aminothiazole Drugs 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- -1 heterocyclic amine Chemical class 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- 206010007559 Cardiac failure congestive Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010019280 Heart failures Diseases 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002934 diuretic Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
Definitions
- This invention relates to substituted benzothiazolesulfonamides and to methods of preparin'g's'aid compounds.
- the compounds of the present invention are, in general, white crystalline solids, soluble inmost organic solvents and having definite melting points.
- the compounds are prepared by dissolving a mercapto-benzothiazole in an aqueous acid solution and passing in chlorine gas to produce the corresponding sulfonyl chloride. This product is then treated with an excess of ammonia in the excess salt and water. These agents, for the most administered in adequate doses.
- R and R are hydrogen, alkyl or heterocyclic radicals.
- the benzene portion of the benzothiazole nucleus may also have present sub- ,requires a large excess of chlorine.
- the reaction time is not particularly critical but chlorine should. be added at such a rate that the temperature does not rise excessively and until an excess is present in the reaction mixture.
- the temperature duringjthe chlorination is preferably maintained within the range of -l0 C. to 25 C. However, during the reaction of the sulfonyl chloride with ammonia or an amine, the
- temperature may be increased to about C., de-
- the compounds of the present invention are active against certain micro-organisms and are also highly efiective as inhibitors of carbonic anhydrase and for this reason, may be effective in the relief of edema associated with. congestive heart failure or in other conditions where inhibition of carbonic anhydrase is useful.
- EXAMPLE 1 V 2benzothiazolesulfonamide parts of Z-mercaptobenzothiazole (powdered) are suspended in a mixture of 550 parts of glacial acetic acid and 1100 parts of water. This mixture is stirred rapidly in a cooling bath while chlorine is introduced in multiple fine "streams at a rapid rate for about three hours. The temperature of the mixture is heldbelow 8-,C. to minimize decomposition. The-chlorine treatment isfcontinued until a test of the suspended solid shows it to be mostly soluble in ethylene chloride; this The crude product is unstable at ordinary temperatures, but
- the filtrate is neutralized with acid; the product slowly crystallizes. It is filtered. and again extracted with dilute alkali and filtered. Acidification of the filtrate again gives slow crystallization.
- the product is filtered, dried, and recrystallized from ethylene chlorigle three times. The pure compound is a while crystalline solid, melting point 148-153 C. (not sharp), with charring and bubbling. As thus produced it is a hemihydrate.
- R is a lower alkyl radical
- R and R are members of the group consisting of hydrogen, lower alkyl and 2-thiazolyl radicals which comprises reacting a mercaptobenzothiazole with chlorine in the presence of an aqueous acid solution and subsequently with a member of the group consisting of ammonia, a lower alkyl amine and Z-aminothiazole.
- a method of preparing Z-benzothiazolesulfon-di-n-butylamide which comprises dissolving 2-mercaptobenzothiazole in aqueous acetic acid solution, passing chlorine into said solution, mixing the resulting product with di-n-butylamine and recovering the said product therefrom.
- a method of preparing N-(Z-thiazolyD- benzothiazole v2 sulfonamide which comprises dissolving Z-mercaptobenzothiazole in aqueous acid solution, passing chlorine into said solution,
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Description
Patented May 6, 1952 BEN ZOTHIAZOLESULFONAMIDES AND METHOD OF PREPARING THE SAME James W. Clapp, Darien, and Richard 0. Roblin, Jr., Riverside, Conn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application April 8, 1950,
Serial No. 154,884
This invention relates to substituted benzothiazolesulfonamides and to methods of preparin'g's'aid compounds.
It is generally recognized that numerous functions and actions of the human body are largely controlled by a wide variety of enzymes. One of these numerous enzymes is called carbonic anhydrase because it is involved in the metabolism of carbon dioxide. This enzyme has other functions too, since it can catalyze the conversion of carbon dioxide to carbonic acid. The excretion of acid by the kidneys is thought to be due to this function of carbonic anhydrase.
The excretion of acid by the kidneys is one method by which the body normally conserves salt. The maintenance of a constant ratio of salt to water in the body is of utmost importance for general health. In some cases, however,-excess salt and water accumulate in the tissues causing a condition which is called edema. It is frequently encountered in association withfcon gestiveheart failure. The excess salt and water cause an uncomfortable swelling of the tissues and place an added strain on the heart. To combat this condition so-called diuretic agents are sometimes used to promote the excretion of the 12 Claims. (Cl. 260306.6)
2 stituents such as halogen, alkyl, alkoxy, hydroxyl and the like.
The compounds of the present invention are, in general, white crystalline solids, soluble inmost organic solvents and having definite melting points.
The compounds are prepared by dissolving a mercapto-benzothiazole in an aqueous acid solution and passing in chlorine gas to produce the corresponding sulfonyl chloride. This product is then treated with an excess of ammonia in the excess salt and water. These agents, for the most administered in adequate doses.
We have now found that substituted benzo- 'thiazolesulfonamides show much greater activity than sulfanilamide in inhibiting carbonic anhydrase. These compounds are new and may be illustrated by the following general formula:
'/CS 02N\ N in which R and R are hydrogen, alkyl or heterocyclic radicals. The benzene portion of the benzothiazole nucleus may also have present sub- ,requires a large excess of chlorine.
form of liquid ammonia or ammonium hydroxide to produce the unsubstituted sulfonamides and with an alkylamine or a heterocyclic amine to produce compounds substituted on the. sulfonamide group. 7 j
The reaction time is not particularly critical but chlorine should. be added at such a rate that the temperature does not rise excessively and until an excess is present in the reaction mixture. The temperature duringjthe chlorination is preferably maintained within the range of -l0 C. to 25 C. However, during the reaction of the sulfonyl chloride with ammonia or an amine, the
= temperature may be increased to about C., de-
pending upon the volatility of the particular amine. Obviously the reaction should be carried out at a temperature below the boiling pointof the amine. Q 4
The compounds of the present invention are active against certain micro-organisms and are also highly efiective as inhibitors of carbonic anhydrase and for this reason, may be effective in the relief of edema associated with. congestive heart failure or in other conditions where inhibition of carbonic anhydrase is useful.
The following examples illustrate the preparation of representative benzothiazolesulfonamides from the corresponding mercaptobenzothiazole. All parts are by weight unless otherwise indicated.
EXAMPLE 1 V 2benzothiazolesulfonamide parts of Z-mercaptobenzothiazole (powdered) are suspended in a mixture of 550 parts of glacial acetic acid and 1100 parts of water. This mixture is stirred rapidly in a cooling bath while chlorine is introduced in multiple fine "streams at a rapid rate for about three hours. The temperature of the mixture is heldbelow 8-,C. to minimize decomposition. The-chlorine treatment isfcontinued until a test of the suspended solid shows it to be mostly soluble in ethylene chloride; this The crude product is unstable at ordinary temperatures, but
is more stable after purification. The crude 2- benzothiazolesulfonyl chloride is then filtered and washed thoroughly with ice-cold water. It can be recrystallized from a large volume of ether or petroleum ether and when pure it forms white crystals, melting point 108-110 C.
30 parts of damp 2-benzothiazolesulfonyl chloride is added to 60 parts of concentrated ammonium hydroxide (d=0.90) with good stirring. The temperature of the mixture is not critical up to at least 40 C. The mixture is stirred for one to two hours, then filtered. The filtrate is treated with activated charcoal, then refiltered, and the product precipitated by neutralization, filtered, washed with water and dried. It is purified by recrystallization from ethylene chloride or from a large volume of water or by repeated solution in dilute alkali and reprecipitation with acid. Impurities are removed from solution with activated charcoal. The pure product is a white crystalline solid, melting point 1'77.5 0., with bubbling. The yield based on 2-mercaptobenzothiazo1e was about 36%.
The yields are improved somewhat by the use of excess anhydrous liquid ammonia for reaction with the sulfonyl chloride. The excess ammonia is then allowed to evaporate and the crude sulfonamide is purified as indicated above. Yields up to 58% (crude) are obtained by this method.
EXAMPLE 2 2-benzothiazolesulfon-n-propylamide Six parts of purified Z-benzothiazolesulfonyl chloride are added gradually to 50 parts of dry n-propylamine, with stirring and chilling. The mixture is stirred for an additional period and the excess amine then evaporated. The residue is triturated with water to produce crystallization. The solid is filtered and washed with water, then redissolved in an excess of dilute sodium hydroxide. The solution is treated with activated charcoal, filtered, and neutralized with acid. The precipitate is filtered, washed with water, and dried, then recrystallized from a large volume of carbon tetrachloride. Yield, 96% of theoretical. The pure product is a white, crystalline solid, melting point 101-101.5 C. It is soluble in ethyl acetate, ethylene chloride, benzene, hot carbon tetrachloride and hot hexane.
EXAMPLE 3 2wbenzothiaeolesulfiovi-di-n-butyiamicie EXAMPLE 4 N-(2 thiazolyZ) benzothiazole- Z-sulfonamide 7.4parts of purified Z-benzothiazole sulfonyl chloride are added gradually to a mixture of 20 parts of 2-aminothiazole and 50 parts of dry pryidine with stirring and chilling. Solution is soon complete. Stirring is continued for about hour without chilling, and the mixture allowed to stand for two days. Water is added, precipitating a gum. The mixture is acidified, and the gum then washed well with water. It is then extracted with dilute alkali, and filtered. The filtrate is neutralized with acid; the product slowly crystallizes. It is filtered. and again extracted with dilute alkali and filtered. Acidification of the filtrate again gives slow crystallization. The product is filtered, dried, and recrystallized from ethylene chlorigle three times. The pure compound is a while crystalline solid, melting point 148-153 C. (not sharp), with charring and bubbling. As thus produced it is a hemihydrate.
We claim:
1. Compounds of the group consisting of those having the general formula:
in which R and R. are members of the group consisting of hydrogen, lower alkyl and Z-thiazolyl radicals.
2. Compounds of the group consisting of those having the general formula:
s p o-s omen in which R is a lower alkyl radical.
3. 2-benzothiazolesulfonamide. 4. 2-benzothiazolesulfon-n-propylamide. 5. Z-benzothiazolesulfon-di-n-butylamide. 6. N- (2-thiazolyl) benzothiazole-2-sulfonamide. 7. A method of preparing compounds having the general formula:
/CSO2N N/ .RI
in which R and R are members of the group consisting of hydrogen, lower alkyl and 2-thiazolyl radicals which comprises reacting a mercaptobenzothiazole with chlorine in the presence of an aqueous acid solution and subsequently with a member of the group consisting of ammonia, a lower alkyl amine and Z-aminothiazole. 8. A method of preparing compounds having the general formula:
mixing the resulting product with N-propylamine and recovering said compound therefrom.
11. A method of preparing Z-benzothiazolesulfon-di-n-butylamide which comprises dissolving 2-mercaptobenzothiazole in aqueous acetic acid solution, passing chlorine into said solution, mixing the resulting product with di-n-butylamine and recovering the said product therefrom.
12. A method of preparing N-(Z-thiazolyD- benzothiazole v2 sulfonamide which comprises dissolving Z-mercaptobenzothiazole in aqueous acid solution, passing chlorine into said solution,
mixing the resulting product with Z-aminothiazole and recovering said product therefrom.
,JAMES W. CLAPP.
RICHARD O. ROBLIN, JR.
REFEREFHJES CITED file of this patent:
Number UNITED STATES PATENTS Name Date Roblin Jan. 9, 1945
Claims (1)
1. COMPOUNDS OF THE GROUP CONSISTING OF THOSE HAVING THE GENERAL FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US154884A US2595334A (en) | 1950-04-08 | 1950-04-08 | Benzothiazolesulfonamides and method of preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US154884A US2595334A (en) | 1950-04-08 | 1950-04-08 | Benzothiazolesulfonamides and method of preparing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2595334A true US2595334A (en) | 1952-05-06 |
Family
ID=22553226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US154884A Expired - Lifetime US2595334A (en) | 1950-04-08 | 1950-04-08 | Benzothiazolesulfonamides and method of preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2595334A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2868800A (en) * | 1954-10-13 | 1959-01-13 | Upjohn Co | 6-ethoxybenzothiazole-2-sulfonamide |
| US2891960A (en) * | 1956-11-03 | 1959-06-23 | Hoechst Ag | Benzothiazol-2-sulfonyl-ureas and a process for their manufacture |
| DE1103341B (en) * | 1957-04-04 | 1961-03-30 | Omikron Gagliardi Societa Di F | Process for the preparation of heterocyclic sulfohalides |
| US2980679A (en) * | 1957-04-04 | 1961-04-18 | Omikron Gagliardi Societa Di F | Process for preparing heterocyclic sulfonamides |
| US3020287A (en) * | 1958-06-05 | 1962-02-06 | Firestone Tire & Rubber Co | Nu-(propynyl)-2-(thiazole) sulfenamides |
| US3139436A (en) * | 1958-06-09 | 1964-06-30 | Merck & Co Inc | Nu-2-benzothiazolylsulfonylbenzamide |
| US3147420A (en) * | 1958-02-10 | 1964-09-01 | Albert A Mros | Electric motor braking control system |
| US3190942A (en) * | 1955-06-17 | 1965-06-22 | Goodyear Tire & Rubber | Cyanoalkyl arylenethiazolesulfenamide accelerators |
| US3216981A (en) * | 1956-10-22 | 1965-11-09 | Monsanto Co | Cyanoalkylthiazolesulfenamides |
| EP0070239A1 (en) * | 1981-07-13 | 1983-01-19 | Merck & Co. Inc. | Benzothiazolesulfonamide derivatives, their preparation and ophthalmic compositions containing said derivatives |
| EP0079269A1 (en) * | 1981-11-03 | 1983-05-18 | Merck & Co. Inc. | Hydroxy-substituted-2-benzothiazolesulfonamide for the topical treatment of elevated intraocular pressure |
| US4416890A (en) * | 1981-07-13 | 1983-11-22 | Merck & Co., Inc. | Benzothiazolesulfonamide derivatives for the topical treatment of elevated intraocular pressure |
| US4426388A (en) | 1982-04-02 | 1984-01-17 | Merck & Co., Inc. | 5-Benzothiazolesulfonamide derivatives for the topical treatment of elevated intraocular pressure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2367058A (en) * | 1942-07-31 | 1945-01-09 | American Cyanamid Co | Pyridine-3-sulphonamide derivatives and processes for their production |
-
1950
- 1950-04-08 US US154884A patent/US2595334A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2367058A (en) * | 1942-07-31 | 1945-01-09 | American Cyanamid Co | Pyridine-3-sulphonamide derivatives and processes for their production |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2868800A (en) * | 1954-10-13 | 1959-01-13 | Upjohn Co | 6-ethoxybenzothiazole-2-sulfonamide |
| US3190942A (en) * | 1955-06-17 | 1965-06-22 | Goodyear Tire & Rubber | Cyanoalkyl arylenethiazolesulfenamide accelerators |
| US3216981A (en) * | 1956-10-22 | 1965-11-09 | Monsanto Co | Cyanoalkylthiazolesulfenamides |
| US2891960A (en) * | 1956-11-03 | 1959-06-23 | Hoechst Ag | Benzothiazol-2-sulfonyl-ureas and a process for their manufacture |
| DE1103341B (en) * | 1957-04-04 | 1961-03-30 | Omikron Gagliardi Societa Di F | Process for the preparation of heterocyclic sulfohalides |
| US2980679A (en) * | 1957-04-04 | 1961-04-18 | Omikron Gagliardi Societa Di F | Process for preparing heterocyclic sulfonamides |
| US3147420A (en) * | 1958-02-10 | 1964-09-01 | Albert A Mros | Electric motor braking control system |
| US3020287A (en) * | 1958-06-05 | 1962-02-06 | Firestone Tire & Rubber Co | Nu-(propynyl)-2-(thiazole) sulfenamides |
| US3139436A (en) * | 1958-06-09 | 1964-06-30 | Merck & Co Inc | Nu-2-benzothiazolylsulfonylbenzamide |
| EP0070239A1 (en) * | 1981-07-13 | 1983-01-19 | Merck & Co. Inc. | Benzothiazolesulfonamide derivatives, their preparation and ophthalmic compositions containing said derivatives |
| US4416890A (en) * | 1981-07-13 | 1983-11-22 | Merck & Co., Inc. | Benzothiazolesulfonamide derivatives for the topical treatment of elevated intraocular pressure |
| EP0079269A1 (en) * | 1981-11-03 | 1983-05-18 | Merck & Co. Inc. | Hydroxy-substituted-2-benzothiazolesulfonamide for the topical treatment of elevated intraocular pressure |
| US4426388A (en) | 1982-04-02 | 1984-01-17 | Merck & Co., Inc. | 5-Benzothiazolesulfonamide derivatives for the topical treatment of elevated intraocular pressure |
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